Waterproofed organic fibrous products



United States Patent 3,454 420 WATERPROOFED ORGAN IC FIBROUS PRODUCTSJacques Pierre Edmond Pechmeze, Paris, and Grard Lon Alphonse Mangeney,Deuil-la-Barre, France, as-

signors to Etablissements Kuhlmann, Paris, France No Drawing. Filed Jan.5, 1966, Ser. No. 518,800

Claims priority, applicatiggoFrance, Jan. 12, 1965,

Int. (:1. ism 1/00 US. Cl. 117-121 7 Claims ABSTRACT OF THE DISCLOSUREThe present invention is concerned with new waterproofing products whichare soluble in those organic solvents used in drycleaning. Such productsare very useful when the cleaned articles have to be made waterproof orkept waterproof.

However, the waterproofing effect has been achieved it is not resistantto, or at least has very poor resistance to, drycleaning hence thenecessity to subject the cleaned article to a subsequent reproofing.This treatment may be effected by means of the ordinary commercialwaterproofing substances, such as those based on emulsions of paraffinwax, stearoylaminomethyl-pyridinium chloride,stearylhydroxymethyl-pyridinium chloride or chromium stearato-chloride.These products must be applied from an aqueous bath. Now the reason forcleaning with solvents is in fact to avoid all manipulation of theclothes in an aqueous medium, which may be harmful to their appearanceand cause felting or shrinking, making them finally unusable. It istherefore of importance to make available to dyers and cleanerswaterproofing substances which are soluble in the solvents which theyuse such as, for example trichloroethylene, perchlorethylene, whitespirit, or dry cleaning solvent.

Such products have already been proposed. There may be mentioned, forexample, organic derivatives of the metals of Groups III or IV, whichmay be in the form of salts of aliphatic acids of high molecular weight,in the form of alcoholates of lower aliphatic alcohols, or in the formof products resulting from the action of aliphatic acids of highmolecular weight on these alcoholates. Waterproofing productsobtained-from alcoholates of polyvalent metals and phosphoric esters, inparticular, have been described, and intended more especially for thewaterproofing of leather.

Among all these products, some have a very low solubility in thedrycleaning solvents and for this reason are diflicult to use. Others,on the contrary, are too soluble in these same solvents with the resultthat during the drying of the treated articles, there is a migration ofthe product on the textile surface, which causes rings and spots.

We have found that waterproofing products having an excellent solubilityin all the solvents used for drycleaning and giving an excellentwaterproofing effect without 3,454,420 Patented July 8, 1969 alterationof the appearance of the treated articles, can be obtained by reactingan acid halide which contains a hydrocarbon chain with 14 to 22inclusive carbon atoms with an alcoholate of a metal of Group III or IVof the Periodic Classification at high temperature.

Examples of acid halide which may be used to carry out the invention arethe chlorides of aliphatic carboxylic acids in which the hydrocarbonchain contains 14 to 22 carbon atoms, such as the higher fatty acids ofnatural origin, the acids resulting from the oxidation of parafiins or0x0 aldehydes, or Koch acids, or the chlorides of alkylsulphonic acidsresulting from the sulphochlorination of parafiins and containing 14 to22 carbon atoms, or the chlorides of phosphoric acid in which one or twoacid groups have been esterified by aliphatic alcohols with ahydrocarbon chain containing 14 to 22 carbon atoms, such as the fattyalcohols of natural origin or the 0x0 alcohols, or the chlorocarbonatesof these same alcohols.

Examples of the metal alcoholates which may be used are the alcoholatesof aluminum, zirconium or titanium, in which the alcoholic radicals arethose of ethyl, isopropyl, propyl, normal butyl, isobutyl, 2-ethylhexyl,lauryl or 0x0 alcohols.

The following procedure may be used for example in the preparation ofthe products of the invention. A solution of a metal alcoholate in aninert solvent, such as for example toluene, is slowly added at lowtemperature, for example below 50 C., to a solution in the same inertsolvent of the acid halide. The amount of metal alcoholate added is suchthat it corresponds to one molecular equivalent per atomic equivalent ofhalogen present in the acid halide. When the addition is completed, thesolvent is driven off by distillation. The mass remaining is then heatedwith agitation at a temperature between C. and 160 C., preferablybetween C. and C. The separation of alkyl halide, the hydrocarbon chainof which corresponds to that of the alcohol of the metal alcoholate, theether corresponding to the same alcohol, as well as the alcoholresulting from the alcoholate is then noted. The heating is interruptedwhen this distillation ceases. The product remaining in the apparatusconstitutes the waterproofing product of the invention.

The waterproofing products thus obtained are soluble intrichlorethylene, perchlorethylene, white spirit, and drycleaningsolvent. Their solutions in these solvents enable textile materials tobe made waterproof or their waterproof properties to be preserved ifthey already possess them. These solutions may also be used for thewaterproofing of other fibrous materials such as leather.

In the following examples which are purely illustrative the parts givenare parts by weight, unless the contrary is indicated.

EXAMPLE 1 151.25 parts of stearoyl chloride and 125 parts by volume oftoluene are introduced into an apparatus fitted with a mechanicalstirrer, a thermometer, a gauge, and a plunging tube. 102 parts ofaluminum isopropylate in solution in 125 parts by volume of toluene areadded by means of the gauge in a period of 4 hours. During this additionthe temperature of the mass rises from 24 C. to 40 C. When theintroduction is completed, the toluene is distilled 3 off under reducedpressure, the temperature of the mass being maintained at 40 C.

After the distillation, a Dean-Stark separating tube is fitted on theapparatus. The exit of the condenser is connected to tubes or flasksplunged into carbon dioxide snow. A stream of nitrogen is passed intothe mass by means of the plunging tube and the mass is heated to 145-150 C. A colourless liquid distils over and is collected in theDean-Stark tube and in the tubes or flasks plunged in the carbon dioxidesnow. 47 parts of a liquid containing isopropyl chloride, isopropylether and isopropanol are obtained. Then the distillation ceases, theheating is interrupted, and the mass is allowed to cool under a streamof nitrogen. The residue consists of 206 parts of a very thick brownliquid containing 6.46% of Cl and 6.30% of Al. The product thus obtainedis excellently soluble in chlorinated solvents and aliphatichydrocarbons, and its solutions give waerproof properties to fabrics.

EXAMPLE 2 The operation is as in Example 1, but the 102 parts ofaluminium isopropylate are replaced by 170 parts of titaniumtetrabutylate. 275 parts of a very thick brown product of resinousconsistency, containing 4.72% of Cl and 8.70% of Ti, are obtained. It isexcellently soluble in all the solvents customarily used for drycleaningIts solutions give excellent waterproof properties to clothes.

EXAMPLE 3 399 parts of stearyl dichlorophosphate (dichlorophosphate oftechnical stearyl alcohol) and 500 parts by volume of toluene areintroduced into an apparatus fitted with a mechanical stirrer, athermometer, a gauge, a plunging tube and a reflux condenser. 408 partsof aluminum isopropylate in solution in 700 parts by volume of tolueneare added by means of the gauge in a period of 4 hours. The temperatureof the mass rises from 20 C. to 55 C. After this introduction, thetoluene is driven off by distilling under reduced pressure, the massbeing heated to 40 C.

When all the toluene has been eliminated, a Dean-Stark separating tubeis fitted on the apparatus and the outlet of the condenser is connectedto bubblers plunged into the carbon dioxide snow. A stream of nitrogenis passed into the mass by means of the plunging tube and thetemperature is raised to 155 C. When the temperature reaches 130 C., acolourless liquid begins to distil and is collected in the Dean-Starktube and in the bubblers. Heating is continued until all distillationceases. 107 parts of this colourless liquid are thus obtained, which onanalysis is found to be composed of isopropyl chloride, isopropyl otherand isopropanol.

After cooling, there remain in the flask 700 parts of a very thick, darkbrown liquid, containing 6.47% of Cl, 4.15% of P and 7.7% of Al, whichis excellently soluble in chlorinated solvents and in aliphatichydrocarbons.

EXAMPLE 4 620.5 parts of octadecyl chlorophosphate and 700 parts byvolume of toluene are introduced into an apparatus identical with thatof Example 3. 204 parts of aluminum isopropylate in solution in 350parts by volume of toluene are added by means of the gauge in a periodof 4 hours. The operation is carried out in the same -way as that ofExample 3. 770 parts of a brown, very thick, resinous product areobtained, which is excellently soluble in the solvents used fordrycleaning and contains 2.30% of Cl, 4.02% of P and 3.50% of Al.

EXAMPLE 5 399 parts of stearyl dichlorophosphate and 500 parts by volumeof toluene are introduced into an apparatus fitted with a mechanicalstirrer, a thermometer, a plung ing tube, and a gauge. A solution of 542parts of zirconium tetraethylate in 700 parts by volume of toluene 4 isintroduced by means of the gauge in ac period of 4 hours. The operationis finished by the method described in Example 3. 830 parts of a dark,resinous, very thick product, soluble in the solvents used fordrycleaning and containing 3.73% of P, 4.2% of Cl and 10.80% of Zr, areobtained.

EXAMPLE 6 A piece of cotton satin weighing 300 g./m. is treated in abath of perchlorethylene containing 30 g. per litre of the waterproofingproduct of Example 1. After drying and returning to the usualatmospheric humidity, the fabric possesses excellent waterproofproperties characterised by a Schmerber figure equal to 350 and aspraytest equal to 100.

EXAMPLE 7 EXAMPLE 8 A piece of cotton satin weighing 300 g./m. istreated in a bath of white spirit containging 10 g. per litre of thewaterproofing product described in Example 4 and 30 g. per litre ofparafiin wax having a melting point between 54 C. and 58 C. Afterdraining, drying and taking up the usual atmospheric humidity, thefabric possesses. waterproof properties characterised by a Schmerberfigure equal to 365 and a spray test equal to 100.

EXAMPLE 9 A piece of calico weighing about g./m. is impregnated in abath of perchlorethylene containing 30 g. per litre of the Waterproofingproduct described in Example 3. After drying and taking up the usualatmospheric humidity, the calico is excellently waterproof. It possessesa Schmerber figure equal to 203 and a spray test equal to 100.

We claim:

1. Organic fibrous materials waterproofed by means of a productresulting from the reaction at high temperature between an acid halidhaving a hydrocarbon chain having from 14 to 22 carbon atoms and a metalalcoholate, the metal of which is selected from the group consisting ofaluminium, zirconium, and titanium, the amount of the said metalalcoholate being in a ratio of 1 molecular equivalent per atomicequivalent of halogen present in the acid halide.

2. The waterproofed fibrous material as defined in claim 1 wherein thealcoholic radical of the metal alcoholate is derived from ethyl, propyl,isopropyl, normal butyl, isobutyl, 2-ethylhexyl, lauryl, or an oxoalcohol.

3. The waterproofed fibrous material as defined in claim 1 wherein theacid halid is stearoyl chloride and the metal alcoholate is aluminiumisopropylate.

4. The waterproofed fibrous material as defined in claim 1 wherein theacid halide is stearyl dichlorophosphate and the metal alcoholate isaluminum isopropylate.

5. The waterproofed fibrous material as defined in claim 1 wherein thereaction between the acid halide and the metal alcoholate is effected ata temperature between C. and 160 C.

6. The waterproofed fibrous material as defined in claim 5 wherein thetemperature is between C. and C.

7. The waterproofed fibrous material as defined in claim 1 wherein saidacid halide is a member selected from the group consisting of 5 6 (a) achloride of an aliphatic carboxylic acid in which References Cited thehydrocarbon chain has from 14 to 22 carbon UNITED STATES PATENTS amms2,774,689 12/1956 Orthner et a1. 117-1355 (-b) a chloride of phosphoricacid in which one or two acid groups have been esterified by analiphatic alco- 5 hol having a hydrocarbon chain of from 14 to 22 WILLIAM D. M ARTIN, Primary Examiner.

2,838,422 6/1958 Orthner et a1 117135.5

carbon atoms, (c) a chloride of an alkylphonic acid having 14 to 22THEODORE DAVIS Amsmm Examine,"

carbon atoms, and U5, C1, X,R

(d) a chlorocarbonate of an aliphatic alcohol having 10 a carbon chainof from 14 to 22 carbon atoms. 143

